Condensation product of 4,4&#39;-dihydroxydiphenyl sulfone, 4,4&#39;-dihydroxydiphenylsulfone sulfonic acid and a lower aldehyde and method of preparation

ABSTRACT

A fixing agent for improving the fastness properties of dyeings on polyamide fibers being a new condensation product of 4,4&#39;-dihydroxydiphenylsulfone, 4,4&#39;-dihydroxydiphenylsulfonesulfonic acid and a lower aliphatic aldehyde, which has a mean molecular weight of about 5,000 to about 30,000 and a ratio of carbon atom content and sulfur atom content of 3.0:1 to 4.8:1, or its metal salt, and when polyamide fibers are treated with the condensation product or its metal salt, or the condensation product in the presence of a salt of metal, at a temperature of 95° to 120° C., the fastness properties, especially wet-fastness properties of dyeings on polyamide fibers are remarkably improved.

BACKGROUND OF THE INVENTION

The present invention relates to a new fixing agent and a process forimproving the fastness properties, especially the wet-fastnessproperties such as the fastness to washing, to hot water, toperspiration or to water, of dyeings on polyamide fibers.

Generally, polyamide fibers are dyed by acid-dyestuffs. However, theemployment of only acid-dyestuffs merely gives very poor fastnessproperties of dyeings. For this reason, there have been adopted avariety of means for improving the fastness properties of dyeings byemploying fixing agents. Among them, a two bath method employing tannicacid and tartar emetic has been known to be the most effective in theviewpoint of fixing dyestuffs on the fibers. This two bath method givesfairly good wet-fastness properties but is poor in the operatingefficiency because of its procedure consisting of two steps, i.e. tannicacid treatment and tartar emetic treatment, which results in a highcost. Further, according to this method, the color matching of dyedfibers is very difficult because the colors of dyeings on fibers areliable to change of shade. The employment of tartar emetic necessitatesan additional facilities for removing toxic tartar emetic from the wastewater of bath. Besides, the supply of tannic acid is unstable from theviewpoint of its raw material and its cost is fairly high.

As one of alternative means for improving the above-mentioned defects ofsuch tannic acid-tartar emetic method, there has been proposed a methodemploying as a fixing agent a condensation product of sulfonated4,4'-dihydroxydiphenylsulfone and a lower aliphatic aldehyde such asformaldehyde or acetaldehyde, for instance, as described in British Pat.No. 975,307. That is to say, in this patent, there is described a methodfor improving the wet-fastness properties of dyeings on polyamide fibersby after-treating a dyed fiber with the condensation product at 80° C.However, even this method is still inferior to the tannic acid-tartaremetic treatment with respect to the effect of fixing dyestuffs onfibers, especially is poor in resistance against steam setting.

OBJECTS OF THE INVENTION

An object of the present invention is to provide a new fixing agent forimproving the fastness properties of dyeings on polyamide fibers.

The other object of the invention is to provide a novel process forpreparing a new fixing agent being capable of fast fixing acid-dyestuffson polyamide fibers.

Another object of the invention is to provide a process for improvingthe fastness properties of dyeings on polyamide fibers.

These and other objects of the invention will be apparent from thefollowing description.

DETAILED DESCRIPTION OF THE INVENTION

The present inventors, as a result of examining the relationship betweenthe constitution of a condensation product of4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfonesulfonicacid and a lower aliphatic aldehyde as a fixing agent and the conditionsfor treating fibers therewith, and the fastness properties of dyeings onpolyamide fibers, have found that the molecular weight of thecondensation product and the numbers of sulfonic acid moiety containedtherein, and the temperature for treating polyamide fibers therewithhave an important effect on the fastness properties, and the employmentof the condensation product in combination with a salt of metal such ascalcium chloride, which is generally capable of forming with a compoundhaving sulfonic acid moiety a metal salt which is slightly soluble inwater, still more improves the fastness properties. That is to say, ithas been found that the superior fastness properties of dyeings onpolyamide fibers which has never been expected from the prior art can beattained by employing as a fixing agent a condensation product of4,4'-dihydroxydiphenylsulfone, its sulfonic acid and a lower aliphaticaldehyde which is characterized by a specified mean molecular weight ofabout 5,000 to about 30,000 and a specified ratio of carbon atom contentand sulfur atom content of 3.0:1 to 4.8:1, or its metal salt prepared byreacting the condensation product with a salt of metal, and treatingpolyamide fibers with the condensation product or its metal salt, orwith condensation product in the presence of a salt of metal, at acomparatively high temperature of 95° to 120° C.

The process of the present invention is entirely different from thatconcretely disclosed in British Pat. No. 975,307 with respect to thefixing agent employed and the temperature for treating polyamide fiberstherewith. The fixing agent employed in this patent is a condensationproduct prepared by sulfonating 1.0 mole of dihydroxydiphenyl sulfonewith 1.0 to 1.5 moles of sulfuric acid and condensing the obtainedsulfonated 4,4'-dihydroxydiphenylsulfone with 0.5 to 1.0 mole ofaldehyde. According to the present inventors' study, the employment ofsuch proportions of the reaction components merely gives a condensationproduct of which portions occupying more than 80% by weight has amolecular weight of 250 to 1,250 and a ratio of carbon atom content andsulfur atom content of 2.8:1 to 2.9:1. In the prior patent, it is alsomentioned that such a known condensation product shows a desirableeffect of improving the fastness properties of dyeings with aftertreatment (different bath-after treatment) at 80° C. In other words,according to the present invention, the fastness properties beingremarkably superior to those obtained by the prior patent can beattained by employing different fixing agent and different temperaturecondition from the prior patent.

In addition, the effect of improving the fastness properties of dyeingsaccording to the present invention is superior to even those achieved bythe tannic acid-tartar emetic method which has been known to be the mostexcellent among the prior art, and the procedures for treating polyamidefibers with the fixing agent in the present invention are simpler thanthose in the tannic acid-tartar emetic method.

In the present invention, it is essential to employ, among condensationproducts of 4,4'-dihydroxydiphenylsulfone, its sulfonic acid and a loweraliphatic aldehyde, the specific condensation product having a meanmolecular weight of about 5,000 to about 30,000 and a ratio of carbonatom content and sulfur atom content of 3.0:1 to 4.8:1. The newcondensation product is soluble in water. The reason why only such aspecific condensation product exhibits an outstanding fixing effect isnot necessarily defined, but such an effect is deemed to be caused bythe fact that the adsorption equilibrium of the specific condensationproduct between its aqueous solution and a polyamide fiber is extremelyfavorable onto the polyamide fiber to result in excellent fixing effect.The condensation products having a molecular weight and a ratio ofcarbon atom content and sulfur atom content deviating from theabove-specified ranges are not preferable since the effects of fixingdyestuffs on polyamide fibers are considerably decreased.

The process of the present invention is applicable to all kinds ofpolyamide fibers, for instance, 6 nylon, 6-6 nylon, 6-10 nylon, andyarns or cloths made of such fibers.

The new fixing agent of the present invention is prepared by treating4,4'-dihydroxydiphenylsulfone with sulfuric acid, condensing theresultant with a lower aliphatic aldehyde, fractionating the obtainedcondensation product to give a fraction having a mean molecular weightof about 5,000 to about 30,000 and a ratio of carbon atom content andsulfur atom content of 3.0:1 to 4.8:1.

In the present invention, it is essential to sulfonate4,4'-dihydroxydiphenylsulfone so that the average molar ratio of4,4'-dihydroxydiphenylsulfonesulfonic acid to free4,4'-dihydroxydiphenylsulfone in the resultant is from 0.015 to 1.1. Inthe case the average number of sulfonic acid moiety deviates from theabove range, it is impossible to obtain a ratio of carbon atom contentand sulfur atom content of 3.0:1 to 4.8:1. The reaction conditions forthe sulfonation are selected so as to satisfy the above-specified degreeof sulfonation. The amount of sulfuric acid employed is preferably from0.8 to 1.0 mole per 1.0 mole of 4,4'-dihydroxydiphenylsulfone. As asulfuric acid, a sulfuric acid having a concentration of 95 to 100% byweight is preferably employed. Preferable reaction temperature for thesulfonation ranges from 110° to 130° C. Preferable reaction period forthe sulfonation ranges from 1 to 5 hours. In the present invention, itis preferable to employ acetic anhydride as a reaction solvent so as tocarry out the sulfonation homogeneously. Preferable amount of aceticanhydride is from 0.7 to 2.0 moles per 1.0 mole of4,4'-dihydroxydiphenylsulfone. Usually, the obtained reaction mixture isemployed as it is for the next step.

The sulfonated product is then condensed with a lower aliphaticaldehyde. Examples of the lower aliphatic aldehyde include formaldehydeand acetaldehyde. Formaldehyde may be employed in a form of its aqueoussolution, i.e. formalin. Preferable concentration of formalin is usuallyfrom 25 to 40% by weight. In the present invention, it is essential toselect the amount of such a lower aliphatic aldehyde from the range of1.0 to 1.2 moles per 1.0 mole of 4,4'-dihydroxydiphenylsulfone. As aresult, the desired fraction having a mean molecular weight of about5,000 to about 30,000 can be obtained in a high yield. In the case theamount of the lower aliphatic aldehyde is less than the above range, theproportion of the fraction having a mean molecular weight of less thanabout 5,000 increases remarkably. On the other hand, in the case theamount of the lower aliphatic aldehyde is more than the above range, theproportion of the fraction having a molecular weight of more than about30,000 increases remarkably.

In general, the condensation reaction is preferably carried out at atemperature of from 90° to 110° C. for 2 to 4 hours under a normalpressure to give a good result. The elevated pressures may be alsoemployed. In the condensation step, the yield of the desired fractionreaches to over 35% by weight calculated on the basis of the totalamount of condensation product. The obtained reaction mixture is usuallyemployed as it is for the next fractionation step.

Thus obtained crude condensation product is then fractionated. As thefractionation method, conventional fractionation method such as gelfiltration method may be employed alone or in combination. In the mostpreferred embodiment of the present invention, the combination of asolvent-treatment method and a gel filtration method is employed becauseof high efficiency. This combination method is explained in detail asfollows:

The crude condensation product is preliminarily fractionated by treatingit with a mixture of water and an organic solvent being not misciblewith water. Preferable examples of the organic solvent include aliphaticesters such as ethyl acetate, n-propyl acetate, isopropyl acetate,diethyl adipate and diethyl succinate, and aliphatic ketones such asdiethyl ketone, methyl isobutyl ketone and methyl n-butyl ketone. Thecrude condensation product is sufficiently agitated together with waterand an organic solvent and then allowed to stand to separate into threelayers. The three layers consist of an organic solvent layer, a waterlayer and a specific layer. The specific layer locates in the lowerlayer with an organic solvent such as ethyl acetate, n-propyl acetate,diethyl succinate, and in the middle layer with methyl isobuthyl ketone.In addition, the specific layer consists of a concentrated aqueoussolution of the desired condensation product. The organic solvent layercontains mainly unreacted starting materials and locates in the upperlayer. The water layer consists of an aqueous solution containing mostlya fraction having a lower molecular weight. The amount of an organicsolvent employed is preferably from 2 to 20 times that of4,4'-dihydroxydiphenylsulfone used as a starting material. Preferableproportion of water and an organic solvent is in a ratio of from 7:3 to1:4 by weight. The specific layer containing the desired fraction istaken out. In this stage, the purity of the desired fraction reaches toover 60% by weight. This fraction may be employed for the next fixingtreatment, as it is or after purification by the following methods.

The separated layer is subjected to further fractionation by a gelfiltration method employing a molecular sieve. Such a gel filtrationmethod is well-known to persons skilled in the art and they will bereadily able to understand the technique in the present invention offractionating the condensation product to obtain a fraction having amean molecular weight of about 5,000 to about 30,000. As a molecularsieve for the gel filtration method, Sephadex G-25 (made by PharmaciaFine Chemicals AB) is preferably employed. According to the gelfiltration, the fractions having a molecular weight of less than about5,000 are removed to give the desired fraction having a mean molecularweight of about 5,000 to about 30,000 and a ratio of carbon atom contentand sulfur atom content of 3.0:1 to 4.8:1 at a purity of 95 to 100%. Thedesired condensation product may be recovered from the aqueous eluate byconcentrating it to dryness or may be employed for the use of theinvention in a form of solution obtained by concentrating the aqueouseluate appropriately.

In the present invention, thus obtained desired condensation product maybe further reacted with a salt of metal. The salt of metal is one whichis generally capable of forming with a compound having sulfonic acidmoiety a metal salt which is slightly soluble in water. Preferableexamples of the salt of metal include calcium chloride, barium chloride,magnesium sulfate, magnesium chloride, aluminum sulfate, aluminumchloride, ferrous sulfate and ferric sulfate. More preferable examplesare calcium chloride, magnesium chloride and magnesium sulfate. Theamount of such a salt of metal employed varies widely depending upon akind of salt of metal employed but at least is selected so that theobtained metal salt is clearly soluble in water in fixing treatment. Ingeneral, the salt of metal is employed in a range of from 1 to 30% byweight, more preferably from 2 to 15% by weight to the amount of thedesired condensation product.

The fixing agent of the present invention, i.e., the above-mentionedcondensation product or its metal salt is employed as follows: In anembodiment, the fixing agent is added to a dyeing bath together with adyestuff. Then the dyeing bath is gradually heated to a temperature of95° to 120° C., more preferably 100° to 110° C. and maintained at thesame temperature for 10 to 30 minutes (same bath-simultaneoustreatment). In other embodiment, after dyeing is completed, the fixingagent is added to a dyeing bath, and then the dyeing bath is heated at atemperature of 95° to 120° C., preferably 100° to 110° C. for 10 to 30minutes (same bath-after treatment). A heating temperature of dyeingbath less than 95° C. is not preferable since the fixing effect of thefixing agent of the present invention cannot be sufficiently exhibited.In another embodiment, the condensation product may be employed togetherwith a salt of metal. As such a salt of metal, the same salt of metal asemployed for preparing the metal salt of the condensation product isalso preferably employed. In that case, the amount of the salt of metalemployed may be the same as that in the case of preparing the metal saltof the condensation product. According to this embodiment, moreexcellent effects can be obtained than those achieved by the singleemployment of the condensation product.

The present invention is more particularly described and explained bymeans of the following illustrative Examples in which all "parts" mean"parts by weight".

EXAMPLE 1

To 300 parts of acetic anhydride was added with agitation 250 parts of4,4'-dihydroxydiphenylsulfone. Thereto was added with agitation 80 partsof a 98% by weight sulfuric acid and the mixture was heated at 120° C.for 2 hours. The resultant was then mixed with 132 parts of a 25% byweight of formalin and heated at 100° C. for 4 hours to give 760 partsof a solution of the condensation product.

To the solution was added 2,300 parts of ethyl acetate and 985 parts ofwater. The mixture was agitated and allowed to stand so as to separateinto three layers. After the separation was completed, the lower layerwas taken out to give 540 parts of an aqueous solution (solid content:35% by weight/volume).

The aqueous solution was passed through a column packed with 300 partsof Sephadex G-25, followed by the successive passing of 500 parts ofwater. The eluate was concentrated to dryness to give 126 parts of apowdery product.

The obtained powdery product has a mean molecular weight of about 8,000and a ratio of carbon atom content and sulfur atom content of 4.5:1. Themolecular weight was determined according to the gel filtration methodemploying Sephadex G-25 as a packing and acid-dyestuffs, C.I. acidorange 7, C.I. acid red 88 and C.I. acid red 114 as standard reagents.The ratio of carbon atoms content and sulfur atom content was determinedby the elementary analysis.

EXAMPLE 2

Into 150 parts of water was dissolved 126 parts of the product obtainedin Example 1. The solution was mixed with 6 parts of magnesium sulfateand agitated for 30 minutes. The reaction mixture was concentrated todryness to give 130 parts of a powdery product.

EXAMPLE 3

To 100 parts of acetic anhydride was added with agitation 250 parts of4,4'-dihydroxydiphenylsulfone. Thereto was added with agitation 90 partsof a 98% by weight sulfuric acid and the mixture was heated at 120° C.for 2 hours. The resultant was then mixed with 132 parts of a 25% byweight formalin and heated at 95° to 100° C. for 2 hours to give 568parts of a solution of the condensation product.

To the solution were added 2,500 parts of methyl isobutyl ketone and1,000 parts of water. The mixture was agitated and allowed to stand soas to separate three layers. After the separation was completed, themiddle layer was taken out to give 550 parts of an aqueous solution(solid content: 35% by weight/volume).

The solution was passed through a column packed with 300 parts ofSephadex G-25, followed by the successive passing of 500 parts of water.The eluate was concentrated to dryness to give 130 parts of a powderyproduct.

The obtained product has a mean molecular weight of 12,000 and a ratioof carbon atom content and sulfur atom content of 4.0:1.

EXAMPLE 4

Into 150 parts of water was dissolved 130 parts of the product obtainedin Example 3. The solution was mixed with 2 parts of calcium chlorideand agitated for 30 minutes. The reaction mixture was concentrated todryness to give 132 parts of a powdery product.

EXAMPLE 5

To 100 parts of acetic anhydride was added with agitation 250 parts of4,4'-dihydroxydiphenylsulfone. Thereto was added with agitation 84 partsof a 98% by weight of sulfuric acid and the mixture was heated at 110°C. for 4 hours. The resultant was then mixed with 125 parts of a 25% byweight formalin and heated at 95° to 100° C. for 4 hours to give 560parts of a solution of the condensation product.

To the solution were added 3,000 parts of n-propyl acetate and 1,000parts of water. The mixture was agitated and allowed to stand so as toseparate into three layers. After the separation was completed, thelower layer was taken out to give 550 parts of an aqueous solution(solid content: 35% by weight/volume).

The aqueous solution was passed through a column packed with 300 partsof Sephadex G-25, followed by the successive passing of 500 parts ofwater. The eluate was concentrated to dryness to give 128 parts of apowdery product.

The obtained product has a mean molecular weight of 10,000 and a ratioof carbon atom content and sulfur atom content of 4.3:1.

EXAMPLE 6

Into 150 parts of water was dissolved 128 parts of the product obtainedin Example 5. The solution was mixed with 5 parts of magnesium chlorideand agitated for 30 minutes. The reaction mixture was concentrated todryness to give 130 parts of a powdery product.

EXAMPLE 7

To 300 parts of acetic anhydride was added with agitation 250 parts of4,4'-dihydroxydiphenylsulfone. Thereto was added with agitation 80 partsof a 98% by weight sulfuric acid and the mixture was heated at 130° C.for 4 hours. The resultant was then mixed with 80 parts of a 37% byweight of formalin and heated at 100° C. for 4 hours.

The obtained condensation product was dissolved into a 50% by weightaqueous solution of acetic acid and the solution was passed through acolumn packed with 500 parts of Sephadex G-25. The fraction eluted witha 50% by weight aqueous solution of acetic acid at a break through pointwas collected and concentrated to dryness to give 150 parts of a powderyproduct.

The obtained product has a mean molecular weight of 10,000 and a ratioof carbon atom content and sulfur atom content of 4.3:1.

COMPARATIVE EXAMPLE 1

To 125 parts of acetic anhydride was added with agitation 250 parts of4,4'-dihydroxydiphenylsulfone. Thereto was added with agitation 125parts of a 98% by weight sulfuric acid and the mixture was heated at 98°to 100° C. for 5 to 6 hours. The resultant was then mixed with 71.5parts of a 30% by weight of formalin and heated at 105° C. for 5 hours.The resultant was concentrated to dryness to give 370 parts of a pastyproduct (known fixing agent).

The obtained product has a mean molecular weight of 1,000 and a ratio ofcarbon atom content and sulfur atom content of 2.8:1.

EXAMPLES 8 TO 13

"Woolic" nylon yarn 80 deniers (made of 6-nylon fiber) was dipped at 20°C. into a dyeing bath containing 2% o.w.f. of C.I. acid blue 129 and 3%o.w.f. of acetic acid (48% by weight) at a liquor-to-goods-ratio of50:1. At the same time, the fixing agent obtained in Example 1 was addedto the dyeing bath so as to reach to 2.5% o.w.f. The dyeing bath wasgradually heated to reach to a temperature of 100° C. and maintained atthe same temperature for 30 minutes. The treated yarn was then rinsedand dried.

The same procedure was repeated with each fixing agent obtained inExamples 2 to 6.

The fastnesses to washing, to hot water, to perspiration and to water ofthe dyed nylon yarns after steam-set at 120° C. for 60 seconds weredetermined according to the methods provided in JIS L 0844 A No. 2, JISL 0845 No. 2, JIS L 0848 A and JIS L 0846 A, respectively. The resultsthereof are shown in Table 1. In Table 1, the numerical values on thecolumn "Fastness" are graduations on the gray scale (provided in JIS L0805) for determining a degree of staining on white cloths which arestained by the dyestuff fallen out from the dyed nylon yarns. Thenumerical value 5 shows the lowest staining and the numerical value 1shows the highest staining.

                  Table 1                                                         ______________________________________                                                   Fastness of dyeing                                                        Fixing                     Perspir-                                    Example                                                                              agent     Washing  Hot water                                                                             ation  Water                                ______________________________________                                         8     Example 1 4 to 5   4 to 5  5      5                                     9     Example 2 4 to 5   4 to 5  5      5                                    10     Example 3 4        4       5      5                                    11     Example 4 4 to 5   4 to 5  5      5                                    12     Example 5 4 to 5   4 to 5  5      5                                    13     Example 6 4 to 5   4 to 5  5      5                                    ______________________________________                                    

EXAMPLE 14

Nylon jersey (made of 6-nylon fiber) was dipped at 25° C. into a dyeingbath containing 2% o.w.f. of C.I. acid blue 129 and 3% o.w.f. of aceticacid (48% by weight) at a liquor-to-goods-ratio of 50:1. At the sametime, the fixing agent obtained in Example 7 was added to the dyeingbath so as to reach to 2.5% o.w.f. The dyeing bath was gradually heatedwith the elevation of 2.5° C. per minute up to 100° C. and maintained atthe same temperature for 60 minutes. The treated cloth was then rinsedand dried. Such a treatment with a fixing agent together with a dyestuffin the same bath on a fiber is hereinafter referred to as "samebath-simultaneous treatment".

EXAMPLE 15

The same nylon jersey employed in Example 14 was dipped into a dyeingbath containing 2% o.w.f. of C.I. acid blue 129 and 3% o.w.f. of aceticacid (48% by weight) at a liquor-to-goods-ratio of 50:1, and dyed at100° C. for 30 minutes. After dyeing, the fixing agent obtained inExample 7 was added to the dyeing bath so as to reach to 2.5% o.w.f. andthe dyeing bath was heated at 100° C. for 30 minutes. The treated clothwas then rinsed and dried. Such a treatment with a fixing agent on afiber previously dyed is hereinafter referred to as "same bath-aftertreatment".

EXAMPLE 16

The procedure of Example 14 was repeated except that magnesium sulfatewas added to the dyeing bath together with the fixing agent obtained inExample 7, the amount of magnesium sulfate being 5% by weight of thefixing agent. (same bath-simultaneous treatment)

EXAMPLE 17

The procedure of Example 15 was repeated except that magnesium sulfatewas added to the dyeing bath after dyeing together with the fixing agentobtained in Example 7, the amount of magnesium sulfate being 5% byweight of the fixing agent. (same bath-after treatment)

COMPARATIVE EXAMPLE 2

The procedure of Example 14 was repeated except that the dyeing bath washeated at 80° C. for 60 minutes. (same bath-simultaneous treatment)

COMPARATIVE EXAMPLE 3

The procedure of Example 15 was repeated except that the dyeing bathafter dyeing was heated at 80° C. for 30 minutes. (same bath-aftertreatment)

COMPARATIVE EXAMPLE 4

The procedure of Example 16 was repeated except that the dyeing bath washeated at 80° C. for 60 minutes. (same bath-simultaneous treatment)

COMPARATIVE EXAMPLE 5

The procedure of Example 17 was repeated except that the dyeing bathafter dyeing was heated at 80° C. for 30 minutes. (same bath-aftertreatment)

COMPARATIVE EXAMPLES 6 TO 7

The same nylon jersey employed in Example 14 was dipped into a dyeingbath containing 2% o.w.f. of C.I. acid blue 129 and 3% o.w.f. of aceticacid (48% by weight) at a liquor-to-goods-ratio of 50:1. The dyeing bathwas gradually heated with the elevetion of 2.5° C. per minute up to 100°C. and maintained at the same temperature for 60 minutes. The dyed clothafter washing with water was dipped into the fixing bath containing thefixing agent obtained in Comparative Example 1 (known fixing agent), of2.5% o.w.f. at a liquor-to-goods-ratio of 30:1 and heated at 100° C. for30 minutes (Comparative Example 6) or 80° C. for 30 minutes (ComparativeExample 7). The treated cloth was then rinsed and dried. (differentbath-after treatment)

COMPARATIVE EXAMPLE 8

The same nylon jersey employed in Example 14 was dipped into a dyeingbath containing 2% o.w.f. of C.I. acid blue 129 and 3% o.w.f. of aceticacid (48% by weight) at a liquor-to-goods-ratio of 50:1. The dyeing bathwas gradually heated with the elevation of 2.5° C. per minute up to 100°C. and maintained at the same temperature for 60 minutes. The dyed clothafter washed with water was dipped into a tannic acid bath of 3% o.w.f.at a liquor-to-goods-ratio of 30:1 and heated at 80° C. for 30 minutes.The cloth treated with tannic acid was washed with water, dipped into atartar emetic bath of 1.5% o.w.f. at a liquor-to-goods-ratio of 30:1 andthen heated at 80° C. for 20 minutes. The treated cloth was rinsed andwashed. (two bath-after treatment)

COMPARATIVE EXAMPLE 9

The same nylon jersey employed in Example 14 was dipped into a dyeingbath containing 2% o.w.f. of C.I. acid blue 129 and 3% o.w.f. of aceticacid (48% by weight) at a liquor-to-goods-ratio of 50:1. The dyeing bathwas gradually heated with the elevation of 2.5° C. per minute up to 100°C. and maintained at the same temperature for 60 minutes. The dyed clothwas rinsed and washed.

The fastnesses of the dyed cloths obtained in Examples 14 to 17 andComparative Examples 2 to 9 were determined in the same manner asdescribed in Examples 8 to 13. The results thereof are shown in Table 2.In Table 2, A, B, C and D in column "Treatment" show the samebath-simultaneous treatment, same bath-after treatment, differentbath-after treatment and two bath-after treatment, respectively.

EXAMPLES 18 TO 21 AND COMPARATIVE EXAMPLES 10 TO 17

The procedures of Examples 14 to 17 and Comparative Examples 2 to 9 wererepeated, respectively, except that "Woolic" nylon yarn of 80 denierswas employed instead of the nylon jersey.

The fastnesses of the dyeings obtained on the nylon yarns are shown inTable 3.

EXAMPLES 22 TO 25 AND COMPARATIVE EXAMPLES 18 TO 25

The procedures of Examples 14 to 17 and Comparative Examples 2 to 9 wererepeated, respectively, except that C.I. acid red 114 of 3% o.w.f. wasemployed instead of C.I. acid blue 129 of 2% o.w.f.

The fastnesses of the dyeings obtained on the nylon cloths are shown inTable 4.

EXAMPLES 26 TO 29 AND COMPARATIVE EXAMPLES 26 TO 33

The procedures of Examples 14 to 17 and Comparative Examples 2 to 9 wererepeated, respectively, except that C.I. acid red 114 of 3% o.w.f. and"Woolic" nylon yarn of 80 deniers were employed instead of C.I. acidblue 129 of 2% o.w.f. and nylon jersey.

The fastnesses of the dyeings obtained on the nylon yarns are shown inTable 5.

EXAMPLES 30 TO 33 AND COMPARATIVE EXAMPLES 34 TO 41

The procedures of Examples 14 to 17 and Comparative Examples 2 to 9 wererepeated, respectively, except that C.I. acid yellow 44 of 3% o.w.f. wasemployed instead of C.I. acid blue of 2% o.w.f.

The fastnesses of the dyeing obtained on the nylon cloths are shown inTable 6.

EXAMPLES 34 TO 37 AND COMPARATIVE EXAMPLES 42 TO 49

The procedures of Examples 14 to 17 and Comparative Examples 2 to 9 wererepeated, respectively, except that C.I. acid yellow 44 of 3% o.w.f. and"Woolic" nylon yarn of 80 deniers were employed instead of C.I. acidblue 129 of 2% o.w.f. and nylon jersey.

The fastnesses of the dyeings obtained on the nylon yarns are shown inTable 7.

EXAMPLES 38 TO 41 AND COMPARATIVE EXAMPLES 50 TO 59

The procedures of Examples 14 to 17 and Comparative Examples 2 to 9 wererepeated, respectively, except that C.I. acid red 257 of 2% o.w.f. wasemployed instead of C.I. acid blue 129 of 2% o.w.f.

The fastnesses of the dyeings obtained on the nylon cloths are shown inTable 8.

EXAMPLES 42 TO 45 AND COMPARATIVE EXAMPLES 58 TO 65

The procedures of Examples 14 to 17 and Comparative Examples 2 to 9 wererepeated, respectively, except that C.I, acid red 257 of 2% o.w.f. and"Woolic" nylon yarns of 80 deniers were employed instead of C.I. acidblue 129 of 2% o.w.f. and nylon jersey.

The fastnesses of the dyeings obtained on the nylon yarns are shown inTable 9.

With respect to the effect of the fixing agent obtained in ComparativeExample 1 (known fixing agent), the treatment "A" or "B" is inferior tothe treatment "C", in either case at 80° C. or at 100° C.

                                      Table 2                                     __________________________________________________________________________                                     Fastness of dyeing                           Example                                                                              Fixing agent                                                                         Metal salt                                                                          Treatment*                                                                          Temp.(°C.)                                                                    Washing                                                                            Hot water                                                                           Perspiration                                                                         Water                      __________________________________________________________________________    14     Example 7                                                                            --    A     100    4    4 to 5                                                                              5      5                          15     Example 7                                                                            --    B     100    4    4 to 5                                                                              5      5                          16     Example 7                                                                            MgSO.sub.4                                                                          A     100    4 to 5                                                                             4 to 5                                                                              5      5                          17     Example 7                                                                            MgSO.sub.4                                                                          B     100    4 to 5                                                                             4 to 5                                                                              5      5                          Comparative                                                                          Example 7                                                                            --    A     80     2    1 to 2                                                                              3      3                          Example 2                                                                     Comparative                                                                          Example 7                                                                            --    B     80     2    1 to 2                                                                              3      3                          Example 3                                                                     Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          A     80     2    1 to 2                                                                              3      3                          Example 4                                                                     Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          B     80     2    1 to 2                                                                              3      3                          Example 5                                                                     Comparative                                                                          Comparative                                                                          --    C     100    1    1     2 to 3 2 to 3                     Example 6                                                                            Example 1                                                              Comparative                                                                          Comparative                                                                          --    C     80     1    1     2 to 3 2 to 3                     Example 7                                                                            Example 1                                                              Comparative                                                                          Tannic acid-                                                                         --    D     80     2 to 3                                                                             2     3 to 4 3 to 4                     Example 8                                                                            tartar emetic                                                          Comparative                                                                          --     --    --    --     1    1     1 to 2 1 to 2                     Example 9                                                                     __________________________________________________________________________     *A: "same bathsimultaneous                                                    B: "same bathafter treatment"-                                                C: "different bathafter treatment"-                                           D: "two bathafter treatment"-                                            

                                      Table 3                                     __________________________________________________________________________                                     Fastness of dyeing                           Example                                                                              Fixing agent                                                                         Metal salt                                                                          Treatment                                                                           Temp.(°C.)                                                                    Washing                                                                            Hot water                                                                           Perspiration                                                                         Water                      __________________________________________________________________________    18     Example 7                                                                            --    A     100    4 to 5                                                                             4 to 5                                                                              5      5                          19     Example 7                                                                            --    B     100    4 to 5                                                                             4 to 5                                                                              5      5                          20     Example 7                                                                            MgSO.sub.4                                                                          A     100    4 to 5                                                                             4 to 5                                                                              5      5                          21     Example 7                                                                            MgSO.sub.4                                                                          B     100    4 to 5                                                                             4 to 5                                                                              5      5                          Comparative                                                                          Example 7                                                                            --    A     80     3    3     4 to 5 4 to 5                     Example 10                                                                    Comparative                                                                          Example 7                                                                            --    B     80     3    3     4 to 5 4 to 5                     Example 11                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          A     80     3    3     4 to 5 4 to 5                     Example 12                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          B     80     3    3     4 to 5 4 to 5                     Example 13                                                                    Comparative                                                                          Comparative                                                                          --    C     100    1 to 2                                                                             1     2 to 3 2 to 3                     Example 14                                                                           Example 1                                                              Comparative                                                                          Comparative                                                                          --    C     80     1 to 2                                                                             1     2 to 3 2 to 3                     Example 15                                                                           Example 1                                                              Comparative                                                                          Tannic acid-                                                                         --    D     80     3 to 4                                                                             2     3 to 4 3 to 4                     Example 16                                                                           tartar emetic                                                          Comparative                                                                          --     --    --    --     2    1     1 to 2 1 to 2                     Example 17                                                                    __________________________________________________________________________

                                      Table 4                                     __________________________________________________________________________                                     Fastness of dyeing                           Example                                                                              Fixing agent                                                                         Metal salt                                                                          Treatment                                                                           Temp.(°C.)                                                                    Washing                                                                            Hot water                                                                           Perspiration                                                                         Water                      __________________________________________________________________________    22     Example 7                                                                            --    A     100    5    4 to 5                                                                              5      5                          23     Example 7                                                                            --    B     100    5    4 to 5                                                                              5      5                          24     Example 7                                                                            MgSO.sub.4                                                                          A     100    5    5     5      5                          25     Example 7                                                                            MgSO.sub.4                                                                          B     100    5    5     5      5                          Comparative                                                                          Example 7                                                                            --    A     80     4    2 to 3                                                                              4      4                          Example 18                                                                    Comparative                                                                          Example 7                                                                            --    B     80     4    2 to 3                                                                              4      4                          Example 19                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          A     80     4    2 to 3                                                                              4      4                          Example 20                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          B     80     4    2 to 3                                                                              4      4                          Example 21                                                                    Comparative                                                                          Comparative                                                                          --    C     100    3    1 to 2                                                                              3      3                          Example 22                                                                           Example 1                                                              Comparative                                                                          Comparative                                                                          --    C     80     2 to 3                                                                             1     2 to 3 2 to 3                     Example 23                                                                           Example 1                                                              Comparative                                                                          Tannic acid-                                                                         --    D     80     5    2 to 3                                                                              4      4                          Example 24                                                                           tartar emetic                                                          Comparative                                                                          --     --    --    --     2    1     1 to 2 1 to 2                     Example 25                                                                    __________________________________________________________________________

                                      Table 5                                     __________________________________________________________________________                                     Fastness of dyeing                           Example                                                                              Fixing agent                                                                         Metal salt                                                                          Treatment                                                                           Temp.(°C.)                                                                    Washing                                                                            Hot water                                                                           Perspiration                                                                         Water                      __________________________________________________________________________    26     Example 7                                                                            --    A     100    5    3 to 4                                                                              4 to 5 4 to 5                     27     Example 7                                                                            --    B     100    5    3 to 4                                                                              4 to 5 4 to 5                     28     Example 7                                                                            MgSO.sub.4                                                                          A     100    5    4     5      5                          29     Example 7                                                                            MgSO.sub.4                                                                          B     100    5    4     4 to 5 4 to 5                     Comparative                                                                          Example 7                                                                            --    A     80     3    1 to 2                                                                              3      3                          Example 26                                                                    Comparative                                                                          Example 7                                                                            --    B     80     3    1 to 2                                                                              3      3                          Example 27                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          A     80     3    1 to 2                                                                              3      3                          Example 28                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          B     80     3    1 to 2                                                                              3      3                          Example 29                                                                    Comparative                                                                          Comparative                                                                          --    C     100    2 to 3                                                                             1 to 2                                                                              3      3                          Example 30                                                                           Example 1                                                              Comparative                                                                          Comparative                                                                          --    C     80     2    1     2 to 3 2 to 3                     Example 31                                                                           Example 1                                                              Comparative                                                                          Tannic acid-                                                                         --    D     80     4 to 5                                                                             2     3 to 4 3 to 4                     Example 32                                                                           tartar emetic                                                          Comparative                                                                          --     --    --    --     2    1     1 to 2 1 to 2                     Example 33                                                                    __________________________________________________________________________

                                      Table 6                                     __________________________________________________________________________                                     Fastness of dyeing                           Example                                                                              Fixing agent                                                                         Metal salt                                                                          Treatment                                                                           Temp.(°C.)                                                                    Washing                                                                            Hot water                                                                           Perspiration                                                                         Water                      __________________________________________________________________________    30     Example 7                                                                            --    A     100    5    4 to 5                                                                               5     5                          31     Example 7                                                                            --    B     100    5    4 to 5                                                                              5      5                          32     Example 7                                                                            MgSO.sub.4                                                                          A     100    5    5     5      5                          33     Example 7                                                                            MgSO.sub.4                                                                          B     100    5    5     5      5                          Comparative                                                                          Example 7                                                                            --    A     80     4 to 5                                                                             3     4 to 5 4 to 5                     Example 34                                                                    Comparative                                                                          Example 7                                                                            --    B     80     4 to 5                                                                             2 to 3                                                                              4      4                          Example 35                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          A     80     4 to 5                                                                             3     4 to 5 4 to 5                     Example 36                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          B     80     4 to 5                                                                             2 to 3                                                                              4      4                          Example 37                                                                    Comparative                                                                          Comparative                                                                          --    C     100    3 to 4                                                                             2     3      3                          Example 38                                                                           Example 1                                                              Comparative                                                                          Comparative                                                                          --    C     80     3 to 4                                                                             2     3      3                          Example 39                                                                           Example 1                                                              Comparative                                                                          Tannic acid-                                                                         --    D     80     5    3     4 to 5 4 to 5                     Example 40                                                                           tartar emetic                                                          Comparative                                                                          --     --    --    --     3    2     1 to 2 1 to 2                     Example 41                                                                    __________________________________________________________________________

                                      Table 7                                     __________________________________________________________________________                                     Fastness of dyeing                           Example                                                                              Fixing agent                                                                         Metal salt                                                                          Treatment                                                                           Temp.(°C.)                                                                    Washing                                                                            Hot water                                                                           Perspiration                                                                         Water                      __________________________________________________________________________    34     Example 7                                                                            --    A     100    5    5     5      5                          35     Example 7                                                                            --    B     100    5    5     5      5                          36     Example 7                                                                            MgSO.sub.4                                                                          A     100    5    5     5      5                          37     Example 7                                                                            MgSO.sub.4                                                                          B     100    5    5     5      5                          Comparative                                                                          Example 7                                                                            --    A     80     4 to 5                                                                             3 to 4                                                                              4 to 5 4 to 5                     Example 42                                                                    Comparative                                                                          Example 7                                                                            --    B     80     4 to 5                                                                             3 to 4                                                                              4 to 5 4 to 5                     Example 43                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          A     80     4 to 5                                                                             3 to 4                                                                              4 to 5 4 to 5                     Example 44                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          B     80     4 to 5                                                                             3 to 4                                                                              4 to 5 4 to 5                     Example 45                                                                    Comparative                                                                          Comparative                                                                          --    C     100    3 to 4                                                                             2 to 3                                                                              4      4                          Example 46                                                                           Example 1                                                              Comparative                                                                          Comparative                                                                          --    C     80     3    2 to 3                                                                              4      4                          Example 47                                                                           Example 1                                                              Comparative                                                                          Tannic acid-                                                                         --    D     80     5    3 to 4                                                                              4 to 5 4 to 5                     Example 48                                                                           tartar emetic                                                          Comparative                                                                          --     --    --    --     3    2     1 to 2 1 to 2                     Example 49                                                                    __________________________________________________________________________

                                      Table 8                                     __________________________________________________________________________                                     Fastness of dyeing                           Example                                                                              Fixing agent                                                                         Metal salt                                                                          Treatment                                                                           Temp.(°C.)                                                                    Washing                                                                            Hot water                                                                           Perspiration                                                                         Water                      __________________________________________________________________________    38     Example 7                                                                            --    A     100    3 to 4                                                                             4     4 to 5 4 to 5                     39     Example 7                                                                            --    B     100    3 to 4                                                                             3     4 to 5 4 to 5                     40     Example 7                                                                            MgSO.sub.4                                                                          A     100    4    3 to 4                                                                              4 to 5 4 to 5                     41     Example 7                                                                            MgSO.sub.4                                                                          B     100    4    3 to 4                                                                              4 to 5 4 to 5                     Comparative                                                                          Example 7                                                                            --    A     80     2    1     2 to 3 2 to 3                     Example 50                                                                    Comparative                                                                          Example 7                                                                            --    B     80     2    1     2 to 3 2 to 3                     Example 51                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          A     80     2    1     2 to 3 2 to 3                     Example 52                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          B     80     2    1     2 to 3 2 to 3                     Example 53                                                                    Comparative                                                                          Comparative                                                                          --    C     100    1    1     2 to 3 2 to 3                     Example 54                                                                           Example 1                                                              Comparative                                                                          Comparative                                                                          --    C     80     1    1     2 to 3 2 to 3                     Example 55                                                                           Example 1                                                              Comparative                                                                          Tannic acid-                                                                         --    D     80     2 to 3                                                                             1     2 to 3 2 to 3                     Example 56                                                                           tartar emetic                                                          Comparative                                                                          --     --    --    --     1    1     1 to 2 1 to 2                     Example 57                                                                    __________________________________________________________________________

                                      Table 9                                     __________________________________________________________________________                                     Fastness of dyeing                           Example                                                                              Fixing agent                                                                         Metal salt                                                                          Treatment                                                                           Temp. (° C.)                                                                   Washing                                                                           Hot water                                                                           Perspiration                                                                         Water                      __________________________________________________________________________    42     Example 7                                                                            --    A     100    4    3 to 4                                                                              4 to 5 4 to 5                     43     Example 7                                                                            --    B     100    4    3 to 4                                                                              4 to 5 4 to 5                     44     Example 7                                                                            MgSO.sub.4                                                                          A     100    4    3 to 4                                                                              4 to 5 4 to 5                     45     Example 7                                                                            MgSO.sub.4                                                                          B     100    4    3 to 4                                                                              4 to 5 4 to 5                     Comparative                                                                          Example 7                                                                            --    A     80     2 to 3                                                                             1     2 to 3 2 to 3                     Example 58                                                                    Comparative                                                                          Example 7                                                                            --    B     80     2 to 3                                                                             1     2 to 3 2 to 3                     Example 59                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          A     80     2 to 3                                                                             1     2 to 3 2 to 3                     Example 60                                                                    Comparative                                                                          Example 7                                                                            MgSO.sub.4                                                                          B     80     2 to 3                                                                             1     2 to 3 2 to 3                     Example 61                                                                    Comparative                                                                          Comparative                                                                          --    C     100    1 to 2                                                                             1     2 to 3 2 to 3                     Example 62                                                                           Example 1                                                              Comparative                                                                          Comparative                                                                          --    C     80     1 to 2                                                                             1     2 to 3 2 to 3                     Example 63                                                                           Example 1                                                              Comparative                                                                          Tannic acid-                                                                         --    D     80     3    1 to 2                                                                              3      3                          Example 64                                                                           tartar emetic                                                          Comparative                                                                           --    --    --    --     1    1     1 to 2 1 to 2                     Example 65                                                                    __________________________________________________________________________

What we claim is:
 1. A condensation product mixture of4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfonesulfonicacid and a lower aliphatic aldehyde, or its salt with a metal selectedfrom the group consisting of calcium, barium, magnesium, aluminum andiron; said 4,4'-dihydroxydiphenylsulfone and4,4'-dihydroxydiphenylsulfonesulfonic acid being a product mixtureformed by treating 1.0 mole of 4,4'-dihydroxydiphenylsulfone with 0.8 to1.0 mole of sulfuric acid so that the average molar ratio of4,4'-dihydroxydiphenylsulfonesulfonic acid to free4,4'-dihydroxydiphenylsulfone in the resultant mixture is from 0.015 to1.1; the condensation product mixture having a mean molecular weight ofabout 5,000 to about 30,000 and a ratio of carbon atom content andsulfur atom content of 3.0:1 to 4.8:1.
 2. The condensation productmixture of claim 1, wherein said condensation product mixture has a meanmolecular weight of about 5,000 to about 15,000 and a ratio of carbonatom content and sulfur atom content of 4.0:1 to 4.4:1.
 3. A process forpreparing a condensation product of 4,4'-dihydroxydiphenylsulfone,4,4'-dihydroxydiphenylsulfonesulfonic acid and a lower aliphaticaldehyde which comprises treating 1.0 mole of4,4'-dihydroxydiphenylsulfone with 0.8 to 1.0 mole of sulfuric acid sothat the average molar ratio of 4,4'-dihydroxydiphenylsulfonesulfonicacid to free 4,4'-dihydroxydiphenylsulfone in the resultant is from0.015 to 1.1, condensing the resultant with 1.0 to 1.2 moles of a loweraliphatic aldehyde, and fractionating the crude condensation product toobtain a condensation product having a mean molecular weight of about5,000 to 30,000 and a ratio of carbon atom content and sulfur atomcontent being 3.0:1 to 4.8:1.
 4. The process of claim 3, wherein saidlower aliphatic aldehyde is formaldehyde or acetaldehyde.
 5. The processof claim 3, wherein said lower aliphatic aldehyde is formaldehyde. 6.The process of claim 3, wherein the treating is carried out at atemperature of 110° to 130° C. for 1 to 5 hours.
 7. The process of claim3, wherein the treating is carried out in the presence of aceticanhydride.
 8. The process of claim 3, wherein the condensing is carriedout at a temperature of 90° to 110° C. for 2 to 4 hours.
 9. The processof claim 3, wherein the fractionating is carried out by treating thecrude condensation product with a mixture of water and an organicsolvent not miscible in water to form three layers, taking out a layercontaining the desired condensation product from said three layers andpassing the layer through a column packed with a molecular sieve to givethe desired condensation product.
 10. The process of claim 9, whereinsaid organic solvent is selected from the group consisting of ethylacetate, n-propyl acetate, isopropyl acetate, diethyl adipate, diethylsuccinate, diethyl ketone, methyl isobutyl ketone and methyl n-butylketone.